Water-soluble glass composition



Parenied Aug. 2s, 1947 2,426,394 WATER-SOLUBLE GLASS COMPOSITION Ralph E. Hsu and Casimir J. Manier, Mount. Lebanon, Pa., assignors to Hall Laboratories, Inc., Pittsburgh, Pa., a corporation of Pennsyl- Vania Application April 15, 1943, Serial No. 483,096 i '6 Claims. l QOuiinvention relates to glassy compositions and more especially to water soluble glasses containing the oxides of potassium, phosphorus and silicon. The compositions of glasses are generally stated as the over-all proportions oi the oxides, and in describing our glassy compositions we will describe them as containing potassium oxide, K20, phosphorus pentoxide, P205, and silica, S102. i

The drawing is a ternary graph of the system K20-P205-Si02 in which the proportions are indicated in mol per cents. For example; the apex represents 100 m'ol per cent of K20. The line along the left-hand boundary of the graph illustrates the varying compositions containing K20 and P205 only. -The potassium metaphosphate composition, KPOa, is at a point representing 50 per cent each of K and P205, since it may be represented as formed of 1 mol each of K20 and 0f P205.

Our invention will iirst beA described with particular reference to glassy compositions consisting principally of &0 and P205 with relatively small modifying S102 additions.

Referring to the drawing, potassium oxide, K20, and phosphorus pentoxlde, P205, form a series of compositions ranging from K20 to P205 along the left-hand boundary ofl the ternary graph. Certain of these compositions appear to be denite chemical compounds which can exist in crystalline form, including the orthophosphate, KaPOr, the pyrophosphate K4P201, and the metaphosphate, KPOs. The orthophosphate and pyrophosphate crystals are readily water soluble and have been used for various purposes, including the making oi. potassium soap solutions. If the orthophosphate and pyrophosphate are cooled, even with drastic quenchingirom a melt. a crystalline product results. The metaphosphate, KPOa, may be obtained in either crystalline or glassy form.l The crystalline form is very diicultly soluble. When a. melt of the meta.- phosphate composition is cooled, it tends to go to the crystalline form unless extremely drastic quenching is employed.` If the melt is subjected to extremely drastic quenching, such, for example, as quenching ln a thin layer between two chilled metal plates, a glass may be obtained. This glass is readily and extensively water solu- 2 ble. It is, however, highly cult to handle and store.

The metaphosphate has a molar ratio of K20 to P205 oi 1:1 and the pyrophosphate a molar ratio of 2:1. Melts having proportions of K20 to P205 between ratios of 1:1 and about 1.8:1 resemble the metaphosphate in that they tend to form a. crystalline mass unless very drastically quenched. Such crystalline mass consists partly of the insoluble crystalline metaphosphate and partly of the soluble crystalline pyrophosphate, the relative amounts depending uponthe proportions of K20 to P205. Such crystalline masses will always contain some of the insoluble crystalline metaphosphate.

Compositions having K20 to P205 molar ratios between 1:1 and about 0.8:1 exhibit properties similar to those of the metaphosphate in that hygroscopic and dim- Ithey tend to become crystalline upon cooling unless drastically quenched, forming a mass consisting principally of insoluble metaphosphate crystals plus a small amount of phosphorus pentoxide. Compositions, however, having a molar ratio of K20 to P205 of less .than about 0.8:1 form glasses upon moderately rapid cooling. the glassforming tendency increasing as the P205 content increases, These glasses, however, are acid in character and are very slowly soluble.

To summarize; there is a range whichincludes the orthophosphate andy pyrophosphate in which the materials are obtained in the form of readily water soluble crystals which are Adefinitely alkaline. There is another range of compositions richer in P205 than the metaphosphate and extending to P205 itself, in which the materials tend to form glasses, but the glasses are distinctly acid and difcultly soluble. There is an intermediate range between the K20 to P205 molar ratios of about 1.8 and 0.8 in which glasses may be formed, but unless the compositions in this range are subjected to extremely drastic quenching they form upon cooling from a melt a crystalline mass which consists principally or partially of insoluble crystalline metaphosphate, the proportion of the metaphosphate depending upon the ratio K20 to P205. These materials range from a slight acidity at the 0.8 ratio through neutrality to moderate alkalinity at the 1.8 ratio, and should be very useful for certain water-conditioning purposes if they could be made soluble, but heretoin the above-mentioned range of'molar ratios of KzO to P205 of about 1.8 to .8 be `modied by the l addition of a small amount of silica, Si02, to the.

melt, readily soluble glass may be obtained with In the graph the portion of the boundary of the area A which lies along the points 6--2-3- 4--5 illustrates in graphic form approximately the minimum amounts of Si02 required to attain compositions which are glass-forming upon moderate chilling between the K2O and P205 ratios of 1.8 and .8 and to render more rapidly soluble the acid glasses in compositions between the ratios of .8 and .6. While, for purposes of graphic illustration, it is necessary to show the boundary of the region A betweenthe points I6---2--3-4-5 -fas a definite une, it wiu be understood that' the line is intended to indicate the order of magnitude moderate chilling. We havel also Afound thatif 1 the potassium phosphates having molar ratlos of fled with the addition of a small amountfof silica to the melt, the rate of solution of the glasses obtained is increased. s v I There is a eutectic between the potassium metaphosphate and pyrophosphate occurring` a. t1 a molar ratio of K2O to P205 of about 1.35. This corresponds to a mol per cent of about 57.5 K and 42.5 of P205. The eutecticis'represented by point I on the graph. Atand in the immediate vicinity ofthis eutectic a minimum of about 2 mol percent of silicafis required Vto..produce a composition which formsa glass uponmoderate chilling, las Aby pouring the melt `in a layer of about 1A; toy; of an inch thick upon a metal plate at room temperature. Such composition is represented by the point 2 and contains in mol per cent 'about 56% KZC. 42% P205and 2%i Si02. At a s 'composition corresponding to the metaphosphate KPOs, a vsomewhat larger amount of silica is required, in the neighborhood of about 4`mol per of the minimum amounts of silica employed, since the minimum amount will vary somewhat depending `upon the-quickness of the chill which can be .obtained in manufacturing operations suchA as by pouring orv dropping a melt of the composition ranges betweenkthe ratios of 1.8 and .8, upon water# or air-cooled plates or conveyors or between cooled rolls and the degree of increased rate of solution 4desired in compositions between the ratios of .8 and.v The maximum amount of silica to be used dependsupon the uses to which such compositions will fall along the curve 6 2- cent. Such composition is represented by theo point 3 and `contains inmol per cent about 48% x20, 53% 'P205 and 4% s ioz. If the molar ratio of K2`0 to P205 is decreased below the 1:1 ratio of the metaphosphaie, tlareqllisite amount of silica tol cause the fo rnri,a'tiiiiiy fa glass upon moderate chilling decreases' uri minimum of v'abouti vmol per cent isrequired ata KzO toPzOs ratio of 0.8. Such composition i'srepresented by the point fand contains in mol percent about 44% K2O, i 55 %v P205 and 1% Si02. If the molar ratio of K20 "to" P205'is decreased below the 0.8:1 ratio, the

L*- silica addition is not required forv its glass-form- 'ing'ffproperties, but is useful in making the glass in such rangevv more soluble. There is, however,

not much usei'n'silica additions to compositions having' a 'KO'to P205 ratio below about .6 because f't e diflicultiesA in dissolving such glasses, even wit silica Fadditions.` and their great acidity. Pointidon the gfraphfrepresents a composition 'liavin'ga KzO to" P205 molar ratio of .6 and con- !f 1'1"'t'aini'hg 5% SiOe Such composition contains in m01 per' cent'fabo ,fl-sica 5 vAt the other side 'of the eutectic point I, namely,

at ratios of K20 to P205 greater than 1.35, the minimumamount' of silica required to form a glass upon moderate quenching increases until in the `neighborhood of y5 mol per cent is required at a -1`.8"ratio.` VSuch composition isrepresented by above about 1.8`1it is practically impossible to obtain melts' whichform glasses even with drastic quenching.v

3-4-5 of the drawing or slightly above it. Where the glass'is to be used primarily for its calcium sequestering or repressing properties, the preferred composition lies at or in the neighborhood of the eutectic having aK20 to P205 molar ratio of y1.35 because of the minimum amount of silica required and because of the lower melting point of the eutectic composition. Where the calcium sequestering or repressing properties of the potassium phosphateglass are the main desideratum.' the silica should not exceed about 7 mol per cent.

The invention, however, is not limited to coinof the region A which lies between the points .6-2f3-4-5 adjacent to the X20-P205 boundv ary, since compositions having much higher proportions of silica are useful for many purposes,

particularly where calcium sequestrationor repression is not especially important.

A For use as a boiler compound where it is desirable to introduce silica into the boiler water, the silica contentmay be increased considerably abovekt Jinimum required for makinga readilylproduc e glass.. Such higher silica compositions-'lie inithejmiddm or toward the right-hand part of the upper region, that is, within the area 6-1-,-l2-32, whereas if alkalinity is the prime consideration, thercompositions will lie toward the rightehand side of the upper part of the region A, that is, within the area 1-8-38-42. The compositions in the lowerpart of the'region A, that is, within the area 3--I 2--9-I ll-l 5-4, and particularly at the left-hand side thereof, that is. within the area 3|2'-I l-'5-4, are acid glasses and may be used for purposes such as the tanning of leather.

The mol percent of KzO. P205 and SiO: in the compositions represented by points, i, 2. 3, 4, and 6 have been given. In order that the mol per cents of compositions represented on the graph by the points may be readily available, the compositions as taken from the graph, are tabu'- lated in the following table. 4

Table Y Mol Per Cent Point X20 P305 Slo,

57. 5 42. 5 none 56 42 2 48 48 4 44 55 1 36 59 5 60 35 6 47 26. 5 26. 5 55 5 39 40 5 55 25 5 70 18 4l 4l 32 34 34 25 l5 60 49 l5 36 Within the area A there are certain compositions at which the constituents can be completely fused at temperatures lower than those of the surrounding compositions. There are, vfor example, ternary eutectics which have relatively low fusion temperatures, and there are also boundaries between the regions of stability for the various compounds which have fusion temperatures lower than those 3f adjoining composition. In general, the compositions which it is preferred to make commercially will coincide with or lie near position sought. The starting materials are fused to a uid melt which is cooled to form the glasses which lie within the area A. Fairly rapid chilling is required to produce glasses in the region at the left-hand side of the area A, particularly in the upper left-hand corner thereof; however, toward the middle and right-hand side of the area, the compositions are readily obtained as glasses with less rapid cooling.

The region C at the apex of the triangular diagram of the drawing is the region in which the materials are crystalline and is therefore excluded. The region D at the lower right-hand corner of the triangle is the region in which glasses may be formed but require excessively high temperatures for their formation. and such glasses are difcultly soluble and is therefore excluded. 'I'he region B at the lower left-hand corner of the triangle is a region in'which glasses may be` acterizing element of the composition. However,

the composition more soluble, particularly in the high silica ranges, decreases the viscosity of the melt-which makes for easier casting and lowers the fusion temperature, which Ais of particular advantage in the vicinity of the higher melting compositions, near the potassium metasilicate, KzSiOs, and potassium disilicate, KaSiaOs, compositions. o The compositions which we desire to cover within the broader scope of our invention fall within the area A of the drawing, although the preferred compositions lie in that part of the area A which is adjacent the line 6-2-3-4-5.

The choice of materials to be fused together to produce the desired composition will be dictated both by the cost of the raw materials and by the convenience in using them. The cheapest source of silica is silica sand, commonly used in the manufacture of silicate glasses; however,

we may use a potassium silicate as a source ofsilica as well as potassium. As our source of potassium oxide we may use potassium chloride, potassium hydroxide or potassium carbonate. The chloride, however, will not be used in the production of the more alkaline products. As a source of P205 we may use the phosphorus peritoxide itself, produced by the burning of phosphorus, or we may use the phosphoric acids derived from P205, or we may use.a.ny suitable potassium phosphate or mixtures thereof. These materials are mixed and fusedin a furnace and maintained in a molten condition until the uniform composition is secured. The melt is taken from the furnace and chilled to form aglass' or super-cooled liquid. The chilling need not beA drastic and may be carried out by the usual commercial methods such as pouring or dropping the material onto a metal plate, a traveling metal conveyor or passing it between metal rolls. The

constituents, KzO, P205 and S102, the compositions may contain other Amaterials so long as they are not subversive to the production of readily water soluble glasses which are useful for the purposes intended; for example, other glassforming oxides, such as boric oxide or metal oxides, added as modifiers, may be incorporated into the melts in minor proportions.

While we have s pecically described our invention, it is to be understood that the invention is not limited to its preferred embodiment or to the details of the foregoing description but may be otherwise embodied and practiced within the scope of the following claims.

We claim:

1. A modified potassium phosphate glass having a molar ratio of K20 to P205 of'between about 1.8:1 to 0.6:1 and containing at least one mol per cent of SiOz.

2. A modified potassium phosphate glass having a molar ratio of KzO to P305 of between about 1.8:1 to 0.6.:1 and containing about 1 to 7 mol per cent of S102.

3. A water-soluble glass consisting essentially of. KzO, P505 and S102, the composition of the glass, when represented in mol per cent being so selected that in the ternary graph of the system,

, S102; 48% X20; 48% P205, 4% S102; 56\%1K20,

4. A water-soluble glass consisting 'essentially of KzO, P205 and Si02, the composition of the glass, when represented in mol per cent being so selectedr that in the ternary graph of the sysv tem, K20-P205-Si02, it lies substantially Within the polygon dened by the points 60% KzO, 35% P205, SiOz; 47% X20, 26.5% P205, 26.5% SiOz; 32% KzO, 34% P205, 34% SiOz; 48% KzO, 48% P205, 4% SiOz; 56% X20, 42% P205, 2% S102.

5. A water-soluble glass consisting essentially of K20, P205 and Si02, the composition of the glass, when represented in mol per cent being so selected that in the ternary graphof the system, K2O-P2O5-Si02, it lies substantially Within the polygon defined by the points 47% K20, 26.5% 25 2,315,995

P205. 26.5% S102; 56% K20, 5% P205, 39% S102: K20, 5% P205, 55% S102; 32% K20, 34% P205;'34% S102.

6. A water-soluble glass consisting essentially of KzO, P205 and S102, the composition of the glass, when represented in mol per cent being so selected that in the ternary graph of the system,

KzO-PzOs-SiOz, it lies substantially within the polygon dened bythe points` 49% KzO, 15% P205, 36% S102; 56%.K20, 5% P205, 39% SiOz; 40% m0, 5% P205, 55% S102; 25% KaO, 5% P205, S102; 25% K2O, 15% P205, 60% SiOn.

RALPH E. HALL. i CASIMJR J. MUNTER.

REFERENCES CITED The following references are of record in the ie of this patent:

UNITED STATES PATENTS Number Name Date 2,304,850 Rice Dec. 15, 1942 2,235,955 Williams Mar. 25, 1941 Williams Apr. 6, 1943 

